Low 4-methylimidazole caramel color class iv production

ABSTRACT

A process of making a caramel color comprising a) mixing a carbohydrate with an ammonia compound and a sulfite compound and at pH from just greater than about 4.0 to about 6.0; and b) heating of the mixture from step a) in a sealed vessel to a temperature of from about 120° C. to about 137° C. and maintaining a temperature in said range for at least about 2 hours, said time and temperature being sufficient to yield a product having a color level of at least about double strength and a level of 4-MeI of less than about 20 ppm, is provided. Also provided is a process of ramped heating which results in a similar caramel color product.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/844,351, filed Sep. 3, 2015, which claims the benefit of U.S.Provisional Application No. 62/076,519, filed Nov. 7, 2014, each ofwhich is hereby incorporated herein by reference for all purposes.

BACKGROUND OF THE INVENTION

4-Methylimidazole (1, hereinafter 4-MeI) is a heterocyclic organicchemical compound formed in the browning of certain foods through theMaillard reaction between carbohydrates and nitrogen compounds. It isfound in roasted foods, grilled meats, coffee, and in types of caramelcolor produced with ammonia-based processes. Scheme 1 sets forth thelikely reactions taking place during the caramel color productionprocess.

Caramel color is one of the oldest and most widely-used food colorings,and is found in almost many commercially produced foods. Caramel coloris manufactured by heating carbohydrates, alone or in the presence ofacids, bases, and/or salts. There are four classes of caramel color,classified according to the reactants used in their manufacture, eachwith its own Class and INS, as listed in Table 1 which follows.

TABLE 1 INS Class No. Name Preparation Uses I 150a Plain caramel Noammonium or sulfite Whiskey and other compounds used high proof alcoholsII 150b Caustic sulfite caramel Sulfite compounds but no Cognac, sherryand ammonium compounds some vinegars used III 150c Ammonia caramel,baker’s Ammonium compounds but Beer, sauces, and caramel, confectioner’sno sulfite compounds used confectionery caramel, or beer caramel IV 150dSulfite ammonia caramel, Both sulfite and ammonium Acidic environmentsacid-proof caramel, or soft- compounds including soft drinks drinkcaramel

Caramel coloring of all types are considered safe and are approved bymany leading regulatory agencies around the world, such as the EuropeanFood Safety Authority (EFSA), the US Food and Drug Administration (FDA),and the Joint FAO/WHO Expert Committee on Food Additives (JECFA).

U.S. Patent Publication No. 2010/0003383 teaches that conventionalproduction of Class IV caramel colors of double strength made at highinitial pH, i.e. a pH of above 5.0, leads to the production of highlevels of 4-MeI. The solution proposed by this publication is theemployment of an initial pH of less than 5.0, e.g. from about 2.0 toabout 4.0.

Co-pending U.S. patent application Ser. No. 14/170,048, filed Jan. 30,2014, teaches the employment of a pH below about 2.0, and especiallypre-heating of a carbohydrate adjusted to a pH of below about 2.0followed by gradual addition of a catalyst comprised of ammoniumcompounds and sulfite compounds, and then heating to a temperaturebetween about 121° C. to about 140° C.

SUMMARY OF THE INVENTION

In a first aspect, this application relates to a process of making acaramel color comprising a) mixing a carbohydrate with an ammoniacompound and a sulfite compound and at pH from just greater than about5.0 to about 6.0, more typically from about 5.0 to about 5.5, and mosttypically from about 5.1 to about 5.3; b) heating the mixture from stepa) in a sealed vessel to a temperature of from about 120° C. to about137° C., more typically from about 125° C. to about 135° C., and mosttypically from about 128° C. to about 133° C., and maintaining atemperature in said range for at least about 1.5 hours, typically atleast about 2 hours, typically from at least about 2.5 hours to about 7hours, more typically from about 2.75 hours to about 6 hours, and mosttypically from about 3 hours to about 5 hours, said time beingsufficient to yield a product having relatively higher color levels(e.g. at least about double strength) and relatively low levels of 4-MeI(e.g. less than about 20 ppm).

In a second aspect, this application relates to a process of making acaramel color comprising:

a) mixing a carbohydrate with an ammonia compound and a sulfite compoundand at pH from just greater than about 4.0 to about 6.0, typically atleast about 4.5, more typically at least about 5.0, typically from about5.1 to about 6.0, and even more typically from about 5.1 to about 5.5;

b) heating the mixture from step a) in a sealed vessel to a firsttemperature of from about 80° C. and about 110° C. and holding at aboutthat first temperature for a first hold time of at least about 30minutes;

c) heating the product from step b) in a sealed vessel to a secondtemperature higher than the first temperature (e.g. at least about 5° C.higher) and less than about 130° C. and maintaining a temperature belowabout 130° C. for a second hold time of at least about 15 minutes;

d) heating the product from step c) in a sealed vessel to a thirdtemperature higher than the second temperature (e.g. at least about 5°C. higher) and less than about 145° C. and for a third hold time of atleast about 30 minutes. Typically, said first hold time is at leastabout twice as long as said third hold time and said third hold time isat least about twice as long as said second hold time.

It has been found that while pH is an important factor in limiting theamount of 4-MeI formed during caramelization to double strength color,the caramelizing temperature has an even greater impact. This is notapparent from the art discussed above and, thus, it was unexpected thatthe employment of a pH above 5.0 would produce double strength Class IVcaramels having relatively low levels of 4-MeI.

DETAILED DESCRIPTION OF THE INVENTION

This application pertains in a first embodiment to a process with afirst step comprising mixing a carbohydrate with an ammonia compound anda sulfite compound, if necessary adjusting the pH to a pH greater thanabout 5.0, typically just greater than about pH 5.0 to about pH 6.0, andthen heating the mixture in a sealed vessel to a temperature of fromabout 120° C. to about 137° C. and holding the mixture within saidtemperature until a product with double strength caramel color isproduced.

In a second embodiment, the first step of the process comprises mixing acarbohydrate with an ammonia compound and a sulfite compound, ifnecessary adjusting the pH to a pH greater than about 5.0, typicallyjust greater than about pH 5.0 to about pH 6.0, then heating the mixturein a sealed vessel to a first elevated temperature, holding the mixtureat said first elevated temperature for a period of time, and thenheating the mixture to a second elevated temperature higher than thefirst elevated temperature and holding the mixture and said secondelevated temperature, thus ramping the temperature of the mixture. Themixture is then held at an elevated temperature until a product with acaramel color with desired color intensity (e.g. double strength) isproduced. The mixture can optionally be ramped to higher temperaturesone or more further times, prior to the product reaching the colorintensity of a double strength caramel color.

The carbohydrate may be derived from any native source, any of which maybe suitable for use herein. Typical sources for the carbohydrate arecereals, tubers, roots, legumes and fruits. The carbohydrate may berefined derived from common sources of sugars such as sugar cane andsugar beet. They may also be derived by processes known in the art fromnative sources of starch such as varieties of corn (maize), pea, potato,sweet potato, banana, barley, wheat, rice, oat, sago, amaranth, tapioca(cassava), arrowroot, canna, and sorghum.

In one embodiment, the carbohydrate is a carbohydrate syrup, and inanother embodiment, a corn syrup, wheat syrup, or mixtures thereof. Inone aspect of the invention, the dextrose equivalent of the carbohydrateis 70 or greater and in another aspect is 80 or greater. As used herein,dextrose equivalent (DE) of a hydrolysis product is defined as itsreducing power as a percentage of the reducing power of pure dextrose.DE may be calculated using the formula:

${{Dextrose}\mspace{14mu}{equivalent}} = \frac{{milligrams}\mspace{14mu}{of}\mspace{14mu}{reducing}\mspace{14mu}{sugar}\mspace{14mu}{as}\mspace{14mu}{dextrose} \times 100}{{milligrams}\mspace{14mu}{of}\mspace{14mu}{dry}\mspace{14mu}{substance}}$

Each starch molecule has one reducing end: therefore DE is inverselyrelated to molecular weight. The DE of anhydrous D-glucose is defined as100 and the DE of unhydrolyzed starch is virtually zero. If thecarbohydrate used is in dry form, the carbohydrate should be mixed intosolution (water) prior to use. In one embodiment, the carbohydrate usedis in a solution of at least about 30 Baumé and in another of at least35 Baumé.

The carbohydrate is mixed with a catalyst comprised ammonia or anammonium compound and a sulfite compound. In one embodiment, thecatalyst is ammonium bisulfite. The pH of the catalyst and/or the pH ofthe blend of acidified carbohydrate and catalyst may be adjusted asnecessary using standard methods known in the art. For example, if thepH is to be adjusted upwards, any alkali such as potassium hydroxide orsodium hydroxide may be used, so long as the alkali is food grade. Ifthe pH is to be adjusted downwards, an acid may be used. In oneembodiment, an inorganic acid is used, and in another embodiment, theacid is selected from the group consisting of hydrochloric acid,sulfuric acid, sulfurous acid, sodium metabisulfite, and phosphorousbased acids (in particular phosphorus and phosphoric acids), so long asthe acid is food grade.

The pH of the mixture can be decreased using methods known in the art.In an embodiment, the pH in step (a) is decreased to just greater than4.0 and in another embodiment greater than or equal to 4.1, or 4.2, orat pHs increasing in increments of 0.1 pH units to about pH 6.0. In anembodiment, the pH in step (a) is no greater than 6.0, and in anotherembodiment no greater than 5.9, or no greater than pHs decreasing frompH 5.9 in increments of 0.1 pH units to about pH 5.5. It should be notedthat the pH will naturally decrease from the initial starting pH and noattempt should be made to arrest such natural decrease, e.g with theaddition of a base or a buffer.

In one embodiment, the ratio of carbohydrate used in step (a) to that ofthe ammonium bisulfite used in step (b) is at least 1 to 3 to about 1 to5 (weight/weight dry basis, hereinafter “w/w db”). In anotherembodiment, the ratio of corn syrup used in step a) to that of theammonium bisulfite used in step b) ranges from about 1 to 3.5 to about 1to 4.5 (w/w db). In another embodiment, the ratio of corn syrup used instep a) to that of the ammonium bisulfite used in step b) ranges fromabout 1 to 4 to about 1 to 4.4 (w/w db).

After the mixture of the carbohydrate and catalyst has been adjusted tothe desired pH, the mixture is subjected to a regime of heating in asealed vessel. In a first embodiment, the mixture is adjusted to a pH ofjust greater than about 5.0 to about 6.0, then heated to a temperaturewithin the temperature range of about 120° C. to about 137° C., and thenheld within that range until the desired strength caramel coloring (e.g.double strength) is produced, but before the levels of 4-MeI areincreased beyond target (e.g. less than about 20 ppm 4-MeI). Typically,the mixture is held at an elevated temperature until a sample of theneutralized product caramel color at 0.1% weight/volume (hereinafter“w/v”) measured at 610 nm is at least double strength, i.e. is at leastabout 0.20 Uabs, more typically at least about 0.21 Uabs, and moretypically at least about 0.22 Uabs, or even at least about 0.23 Uabs.The color intensity is measured by the test procedure described in themonograph prepared at the 55th JECFA (2000) and published in FNP 52 Add8 (2000), the disclosure of which is incorporated herein by referencethereto.

In a second embodiment, the contents of the seal vessel are subject to aregime of one or more periods of ramped heating and maintaining orholding at an elevated temperature below about 120° C., followedultimately by final ramping and heating at an elevated temperature thatis below about 145° C. While maintaining the temperature of the mixtureat a specific elevated hold temperature is convenient from theperspective of a simplified process, it is not technically necessary tostrictly regulate the elevated temperature so long as the temperature ismaintained below the upper limits as specified in the summary of theinvention, above. Likewise, the specific hold times at each elevatedtemperature are not critical so long as the times at temperatures aremaintained within the ranges specified in the summary above.

The temperature of the reaction mixture in the final hold step ismaintained until the desired strength caramel coloring (e.g. doublestrength) is produced, but before the levels of 4-MeI are increasedbeyond target. In one embodiment, the time of the final hold is at least30 minutes. In an embodiment, the time of step (e) is no more than 150minutes, in yet another embodiment no more than 90 minutes.

In one aspect, this application relates to a process of making a caramelcolor comprising a) mixing a carbohydrate with an ammonia compound and asulfite compound and at pH from just greater than about 4.0 to about6.0; b) heating the mixture from step a) in a sealed vessel to a firsttemperature of from about 45° C. to about 75° C. and maintaining atemperature below about 75° C. for at least about 15 minutes, typicallyfrom at least about 30 minutes to about 2 hours; c) heating the productfrom step b) in a sealed vessel to a second temperature higher than thefirst temperature (e.g. at least about 5° C. higher) and less than about85° C. and maintaining a temperature below about 85° C. for at leastabout 15 minutes, typically from at least about 30 minutes to about 2hours; d) heating the product from step c) in a sealed vessel to a thirdtemperature higher than the second temperature (e.g. at least about 5°C. higher) and less than about 100° C. and for at least about 30minutes, typically from at least about 1 hour to about 3 hours; e)heating the product from step d) in a sealed vessel to a fourthtemperature higher than the third temperature (e.g. at least about 5° C.higher) and less than about 130° C. and maintaining a temperature belowabout 130° C. for at least about 15 minutes, typically from at leastabout 30 minutes to about 1 hour; and f) heating the product from stepe) in a sealed vessel to a fifth temperature higher than the fourthtemperature (e.g. at least about 5° C. higher) and maintaining themixture of step d) at a temperature from about 130° C. to about 145° C.over a time from about 15 minutes to about 2 hours, said times andtemperatures being sufficient to produce a product caramel coloringhaving the desired levels of both color and 4-MeI.

As stated above, it has been found that while pH is an important factorin limiting the amount of 4-MeI formed during caramelization to doublestrength color, the caramelizing temperature has an even greater impact.This is not apparent from the art and, thus, it was unexpected that theemployment of a pH above 4.0 would produce double strength Class IVcaramels having low levels of 4-MeI. It was found that the use of arelatively lower hold temperature and/or a ramped heating regime(particularly one with a relatively longer hold time between about 80°C. and about 110° C. and then again between about 130° C. and about 145°C., with the hold time between about 130° C. and 145° C., being for ashorter time than the time at 80° C. to about 110° C.) allows for theproduction of double strength Class IV caramels having low levels of4-MeI while employing pHs above 4.0. Without wishing to be bound by anyparticular theory, it is believed that the comparative kinetics andcomparative thermodynamic of the various reactions which form colorbodies and the various reactions leading to the formation of 4-MeI andits starting compounds allow for the unexpected “sweet spot” ofrelatively lower temperatures and higher pHs that was discovered and isdescribed herein.

The vessel employed should be a sealed vessel capable of pressurizationto the pressures that are anticipated during the reaction, e.g. fromabout 3.0 Kg/cm² to about 5.3 Kg/cm². Once the desired caramel color isobtained, the pressure is released to ambient pressure. In oneembodiment, the temperature is decreased with the reduction of pressureto a temperature of no more than about 100° C. and in another embodimentto a temperature of no more than 90° C.

The resultant caramel color may be adjusted using standard methods knownin the art. The degree Baumé and/or pH may be adjusted.

The resultant caramel color obtained by this process typically has aviscosity of less than 500 cps measured at 23° C. In another embodiment,the viscosity of the resultant caramel color obtained by this process isless than 200 cps measured at 23° C. In yet another embodiment, theviscosity of the resultant caramel color obtained by this process isless than 100 cps measured at 23° C. Viscosity, as used herein, ismeasured by Brookfield Viscometer using the analytical procedure setforth in the Examples section and is measured on caramel color adjustedto a Baumé of 30.0-31.0 at 15.5° C.

In one embodiment, the viscosity of caramel color obtained by thisprocess is typically stable at a storage temperature of 40° C. for atleast 8 weeks, and in another embodiment, the viscosity of caramel colorobtained by this process is stable at a storage temperature of 40° C.for at least 12 weeks. As used herein, a stable viscosity is one whichchanges by no more than 50 cps from the initial viscosity (that prior tostorage).

The resultant caramel color can be of different color intensitiesdepending upon the cooking time, temperature and catalyst concentration.In one embodiment, the caramel color at 0.1% (w/v) measured at 610 nm isat least about 0.2 Uabs and in another embodiment is at least about 0.21Uabs. Typically, the caramel color at 0.1% (w/v) measured at 610 nm isat least about 0.22 Uabs, and more typically at least about 0.23 Uabs.In one embodiment, the caramel color at 0.1% (w/v) measured at 610 nm isno more than 0.25 Uabs and in another embodiment is no more than 0.24Uabs.

The resultant caramel color (at a Baumé of 30.0-31.0 at 15.5° C.) has a4-MeI content less than 20 ppm, in one embodiment less than 15 ppm, inanother embodiment less than 10 ppm and in still yet another embodimentless than 5 ppm. The 4-MeI content should be measured by liquidchromatography/mass spectrometry (LC-MS/MS) or gas chromatography/massspectrometry on the reaction mixture as it comes from the sealed vessel(“as is”). The DE can be measured as described in “ISI 28-leDetermination of Reducing Sugar, DE by Luff-Schoorl's Method” publishedby the International Starch Institute, Science Park Aarhus, Denmark, asRev. LT Jan. 22, 2002.

EXAMPLES Color Intensity Evaluation.

For the purpose of this specification, Colour Intensity is defined asthe absorbance of a 0.1% (w/v) solution of Caramel Colour solids inwater in a 1 cm cell at 610 nm.

Procedure:

Transfer 100 mg of Caramel Colour into a 100 ml volumetric flask, diluteto volume with water, mix and centrifuge if the solution is cloudy.Determine the absorbance (A₆₁₀) of the clear solution in a 1 cm cell at610 nm with a suitable spectrophotometer previously standardized usingwater as a reference.

Brookfield Viscosity Evaluation Procedure.

The viscosity and appearance of samples were assessed using a BrookfieldViscometer Model RV-DV-II+PRO, with standard needle and a laboratorysupport, and Fluid 100, which is a standard of calibration available ofsilicone of 100 cps (available from Brookfield Engineering Laboratories,Inc., 240 Cushing St., Stoughton, Mass., USA). About 500 mL of caramelcolor sample was pour into a 600 mL stainless steel vessel, sliding thevessel wall to prevent the formation of air bubbles. In a recirculatingwater bath at a controlled temperature, the container with the samplewas placed to warm up to 30° C., verifying the temperature with the helpof a digital or mercury thermometer. The viscometer was placed into theholder and adjusted to the proper height. The needle viscometer wascarefully connected by holding the shaft tightly and screwing the needleto the left. The guard was positioned and assembly level. The guard andcaramel color needle were introduced at an angle to prevent theformation of air bubbles. Adjusted the apparatus so that the notch wason the surface of the sample. The viscometer was started at 20 or 50 rpmand spindle number 1 or 2 was used. The viscosity was read and reported.

Examples 1-15 and Comparative Example A

1. Mix glucose corn syrup (331.7 g, 42.7° Be, 77.5DE, pH 4.7) withammonium bisulfate (79.6 g, 68% solids content, pH 5.7).2. Adjust pH of the mixture to the value (±0.1) set forth in Table 2 orTable 3 with a mineral acid (e.g. hydrochloric or phosphoric acid).3. Heat mixture in a sealed vessel to the temperature (±1° C.) set forthin Table 2 or Table 3.4. Allow the reaction to proceed at this temperature until the desiredcolor absorbance set forth in Table 2 or Table 3 is obtained.5. After the desired color absorbance is obtained, stop the reactionwith a flash step.6. Cool and adjust caramel color pH to 3.0 and density to 1.27 g/ml.

TABLE 2 Color Adjusted Time of Intensity Viscosity pH after HeatingHeating (0.1% w/v, 4-MEI* (cP) @ Example mixing Profile (min.) 610 nm)(ppm) Temp. A 6.5 Heating from 184-239 0.224-0.230 ~400 to 100 @ 30° C. 23° C. to 159° C. 600 1 5.9 Heating from 196 0.220 29.9 76 @ 23° C. 23°C. to 133° C. 2 5.5 Heating from 177 0.227 11.1 80.8 @ 23° C.   23° C.to 133° C. 3 5.2 Heating from 181 0.222  7.4 76 @ 23° C. 23° C. to 133°C. 4 5.1 Heating from 181 0.245  7.2 102.8 @ 23° C.   23° C. to 133° C.5 5.1 Heating from 240 >0.200  13.4/14   78 @ 30° C. 23° C. to 133° C. 64.5 Heating from 300 0.215 10.9/11.0 72 @ 30° C. 23° C. to 133° C. 7 4.5Heating from 280 0.214 11.8/13.0 69 @ 30° C. 23° C. to 128° C. *Measured“as is” by Liquid Chromatography/Mass Spectrometry (LC-MS/MS) exceptExample 1 was measured “as is” by Gas Chromatography/Mass Spectrometry(GC-MS).

TABLE 3 Color Adjusted Intensity Viscosity pH after (0.1% w/v, 4-MEI*(cP) @ Example mixing Heating Profile ° C. (for min.) 610 nm) (ppm)Temp. A 6.5 Heating from 23° C. to 159° C. (184-239)  0.224- ~400 to 100@ 0.230 600 30° C.  5 5.5 60° C. (over-weekend) 95° C. (120 min), 0.25516.7  ≤300 @ 105° C. (60 min), 115° C. (60 min), 125° C. 30° C. (30min), 142° C. (90 min)  6 5.5 68° C. (60 min), 85° C. (60 min), 95° C.0.241 15.3  115.6 @ (120 min), 105° C. (60 min), 115° C. 23° C. (30min), 125° C. (30 min), 142° C. (90 min)  7 5.5 68° C. (60 min), 85° C.(60 min), 95° C. 0.229 14.9  ≤300 @ (120 min), 105° C. (60 min), 115° C.30° C. (30 min), 125° C. (30 min), 142° C. (90 min)  8 5.1 60° C. (30min), 68° C. (60 min), 78° C. 0.229 10.8  125.6 @ (30 min), 85° C. (60min), 90° C. (60 min), 23° C. 95° C. (120 min), 100° C. (60 min), 105°C. (60 min), 115° C. (30 min), 125° C. (30 min), 138° C. (90 min)  9 5.160° C. (30 min), 68° C. (60 min), 78° C. 0.241 9.6 154.0 @ (30 min), 85°C. (60 min), 90° C. (60 min), 23° C. 95° C. (120 min), 100° C. (60 min),105° C. (60 min), 115° C. (30 min), 125° C. (30 min), 138° C. (90 min)60° C. (30 min), 68° C. (60 min), 78° C. (30 min), 85° C. (60 min), 90°C. (60 min), 10 5.1 95° C. (120 min), 100° C. (60 min), 105° C. 0.22910.8  125.6 @ (60 min), 115° C. (30 min), 125° C. 23° C. (30 min), 138°C. (90 min) 68° C. (60 min), 85° C. (60 min), 95° C. 11 4.5 (120 min),105° C. (60 min), 115° C. >0.200  6.9 121.2 @ (30 min), 125° C. (30min), 138° C. 30° C. (100 min) 12 4.5 68° C. (60 min), 85° C. (60 min),95° C. 0.223 7.1 196.2 @ (120 min), 105° C. (60 min), 115° C. 23° C. (30min), 125° C. (30 min), 138° C. (100 min) *Measured “as is” by LiquidChromatography/Mass Spectrometry (LC-MS/MS) except Example 12 wasmeasured “as is” by Gas Chromatography/Mass Spectrometry (GC-MS).

While particular embodiments of the present application have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the application. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this application. Allamounts, parts and percentages are by weight unless otherwise indicatedin context.

1. A process of making a caramel color comprising: a) mixing a carbohydrate with an ammonia compound and a sulfite compound and at pH from just greater than about 5.1 to about 6.0; and b) heating the mixture from step a) in a sealed vessel to a temperature of from about 120° C. to about 137° C. and maintaining a temperature in said range for at least about 1.5 hours, wherein said time and temperature are sufficient to yield a product having a color level of at least about double strength and a level of 4-methylimidazole (4-MeI) of less than about 15 ppm.
 2. The process of claim 1, wherein the temperature is from about 125° C. to about 135° C.
 3. The process of claim 1, wherein the temperature is from about 128° C. to about 133° C.
 4. The process of claim 1, wherein the time of heating and maintaining is at least about 2 hours.
 5. The process of claim 1, wherein the time of heating and maintaining is from about 2.5 hours to about 7 hours.
 6. The process of claim 1, wherein the time of heating and maintaining is from about 3 hours to about 5 hours.
 7. The process of claim 1, wherein the pH is from about 5.1 to about 5.7.
 8. The process of claim 1, wherein the pH is from about 5.1 to about 5.5.
 9. The process of claim 1, wherein the caramel color at 0.1% w/v measured at 610 nm is at least about 0.2.
 10. The process of claim 1, wherein the caramel color at 0.1% w/v measured at 610 nm is at least about 0.21 Uabs.
 11. The process of claim 1, wherein the caramel color at 0.1% w/v measured at 610 nm is at least about 0.23.
 12. (canceled)
 13. The process of claim 1, wherein the 4-MeI content is less than 10 ppm.
 14. A process of making a caramel color comprising: a) mixing a carbohydrate with an ammonia compound and a sulfite compound and at pH from 5.1 to about 6.0; b) heating the mixture from step a) in a sealed vessel to a first temperature of from about 80° C. and about 110° C. and holding at about that first temperature for a first hold time of at least about 30 minutes; c) heating the product from step b) in a sealed vessel to a second temperature higher than the first temperature and less than about 130° C. and maintaining a temperature below about 130° C. for a second hold time of at least about 15 minutes; d) heating the product from step c) in a sealed vessel to a third temperature higher than the second temperature and less than about 145° C. and for a third hold time of at least about 30 minutes.
 15. The process of claim 14, wherein said first hold time is at least about twice as long as said third hold time and said third hold time is at least about twice as long as said second hold time. 16-17. (canceled)
 18. The process of claim 14, wherein said pH is from about 5.1 to about 5.5. 19-20. (canceled) 